Information recording medium and method of manufacturing the same

ABSTRACT

An information recording medium that is excellent in repeated-rewriting performance and is deteriorated less in crystallization sensitivity with time is provided, with respect to which high density recording can be carried out. A method of manufacturing the same also is provided. The information recording medium includes a substrate and a recording layer disposed above the substrate. The recording layer contains, as constituent elements, Ge, Sb, Te, Sn, and at least one element M selected from Ag, Al, Cr, Mn, and N and is transformed in phase reversibly between a crystal phase and an amorphous phase by an irradiation of an energy beam.

This application is a divisional of application Ser. No. 09/801,977,filed Mar. 8, 2001, which application(s) are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to an information recordingmedium with respect to which information can be optically recorded,erased, rewritten, and reproduced, and to a method of manufacturing thesame.

2. Related Background Art

In a phase-change information recording medium, information is recorded,erased, and rewritten using a recording layer that is transformed inphase reversibly between a crystal phase and an amorphous phase. Whenthis recording layer is irradiated with a high power laser beam and thenis cooled rapidly, a portion thus irradiated is changed to be in anamorphous state and as a result, a recording mark is formed. Similarly,when an amorphous portion of the recording layer is irradiated with alow power laser beam and then is cooled slowly, the portion thusirradiated is changed to be in a crystal phase and as a result, arecording mark is erased. Therefore, in the phase-change informationrecording medium, the recording layer is irradiated with laser beamshaving powers modulated between a high power level and a low powerlevel, so that new information can be rewritten while previousinformation is erased.

When information is to be rewritten, atoms move within the recordinglayer as the recording layer is transformed in phase between the crystalphase and the amorphous phase. As a result, in a conventionalinformation recording medium, when rewriting is repeated, atoms may beconcentrated locally to vary the thickness of the recording layer andthis may cause deterioration in signal quality in some cases. Suchrepeated-rewriting performance is deteriorated particularly with theincrease in recording density. The reason is that when the recordingdensity increases, the intervals between adjacent recording marks areshortened and therefore the influence of the concentration of atoms inthe adjacent recording marks increases.

In order to prevent the repeated-rewriting performance from beingdeteriorated, it is necessary to reduce the thickness of the recordinglayer to suppress the atom movement. In addition, the reduction inthickness of the recording layer also is a technique required to obtaina high density information recording medium with two recording layers.However, the reduction in thickness of the recording layer makes itdifficult for atoms to move. Therefore, the crystallization rate of therecording layer decreases. The decrease in crystallization rate resultsin the deterioration in signal quality in a high density informationrecording medium in which small recording marks must be recorded in ashort time. In addition, when the crystallization rate decreases,deterioration in crystallization sensitivity with time and that inerasing rate with time tend to occur. In other words, with the increasein recording density, it becomes difficult to achieve both theimprovement in the repeated-rewriting performance and the suppression ofthe deterioration in crystallization sensitivity with time.

In order to improve the repeated-rewriting performance, a recordinglayer containing Te, Ge, Sn, and Sb has been reported (see JP2(1990)-147289 A).

In the above-mentioned conventional recording layer, however, thecrystallization rate was high but the repeated-rewriting performance andlong-term reliability of the crystallization sensitivity in high densityrecording were not sufficiently high.

SUMMARY OF THE INVENTION

Therefore, with the foregoing in mind, it is an object of the presentinvention to provide an information recording medium that allows highdensity recording to be carried out, is excellent in repeated-rewritingperformance, and is deteriorated less in crystallization sensitivitywith time, and to provide a method of manufacturing the same.

In order to achieve the above-mentioned object, an information recordingmedium of the present invention includes a substrate and a recordinglayer disposed above the substrate. The recording layer contains, asconstituent elements, Ge, Sb, Te, Sn, and at least one element Mselected from Ag, Al, Cr, Mn, and N. The term “constituent element”denotes an element indispensable for allowing a property of a materialcontaining the element to be expressed. It is preferable that therecording layer consists essentially of Ge, Sb, Te, Sn, and at least oneelement M. The recording layer is transformed in phase reversiblybetween a crystal phase and an amorphous phase by an irradiation ofenergy beams. According to the information recording medium, it ispossible to obtain an information recording medium that allows highdensity recording to be carried out, is excellent in therepeated-rewriting performance, and is deteriorated less incrystallization sensitivity with time.

In the above-mentioned information recording medium, the recording layermay be formed of a material expressed by a composition formula of[(Ge, Sn)_(A)Sb₂Te_(3+A)]_(100−B)M_(B),where 0<A≦10 and 0<B≦20. When A≦10, the repeated-rewriting performancecan be prevented from deteriorating. When B≦20, the deterioration incrystallization sensitivity with time can be prevented from worsening.

In the above-mentioned information recording medium, the content of Snin the recording layer may be 2 atom. % to 20 atom. %. When the Sncontent is set to be at least 2 atom. %, a sufficiently highcrystallization rate can be obtained. In addition, when the Sn contentis set to be not more than 20 atom. %, it is possible to increase theratio of a quantity of reflected light when the recording layer is in acrystal phase to a quantity of reflected light when the recording layeris in an amorphous phase.

In the above-mentioned information recording medium, the recording layermay have a thickness of 5 nm to 15 nm. When the thickness of therecording layer is set to be at least 5 nm, the recording layer can bechanged to be in a crystal phase easily. In addition, when the thicknessof the recording layer is set to be not more than 15 nm, therepeated-rewriting performance can be prevented from deteriorating.

The information recording medium further may include a first protectivelayer, a second protective layer, and a reflective layer. The firstprotective layer, the recording layer, the second protective layer, andthe reflective layer may be formed sequentially on the substrate. Inthis case, the information recording medium further may include aninterface layer disposed in at least one position selected from aposition between the first protective layer and the recording layer anda position between the second protective layer and the recording layer.Furthermore, the information recording medium further may include anoptical absorption compensation layer disposed between the secondprotective layer and the reflective layer.

The information recording medium further may include a first protectivelayer, a second protective layer, and a reflective layer. The reflectivelayer, the second protective layer, the recording layer, and the firstprotective layer may be formed sequentially on the substrate. Accordingto the above-mentioned configuration, an information recording mediumcan be obtained that allows particularly high density recording to becarried out. In this case, the information recording medium further mayinclude an interface layer disposed in at least one position selectedfrom a position between the first protective layer and the recordinglayer and a position between the second protective layer and therecording layer. Moreover, the information recording medium further mayinclude an optical absorption compensation layer disposed between thereflective layer and the second protective layer.

A method of manufacturing an information recording medium according tothe present invention is directed to a method of manufacturing aninformation recording medium provided with a substrate and a recordinglayer disposed above the substrate. The method includes forming therecording layer by a vapor deposition method. The recording layercontains, as constituent elements, Ge, Sb, Te, Sn, and at least oneelement M selected from Ag, Al, Cr, Mn, and N. The recording layer istransformed in phase reversibly between a crystal phase and an amorphousphase by an irradiation of energy beams. According to the manufacturingmethod, an information recording medium of the present invention can bemanufactured easily.

In the above-mentioned manufacturing method, the vapor deposition methodmay be at least one method selected from a vacuum evaporation method, asputtering method, an ion plating method, a chemical vapor deposition,and a molecular beam epitaxy.

In the above-mentioned manufacturing method, the vapor deposition methodmay be a sputtering method using a gas containing at least one gasselected from nitrogen gas and oxygen gas and one rare gas selected fromargon and krypton.

In the manufacturing method, the recording layer may be deposited at adeposition rate of 0.5 nm/sec to 5 nm/sec. According to theconfiguration described above, a recording layer in the amorphous statecan be deposited.

In the manufacturing method, the recording layer may have a thickness of5 nm to 15 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a partial sectional view showing an example of an informationrecording medium according to the present invention.

FIG. 2 is a partial sectional view showing another example of aninformation recording medium according to the present invention.

FIG. 3 is a schematic view of a recording/reproducing device used forevaluation of information recording media.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention are described with reference to thedrawings as follows.

Embodiment 1

In Embodiment 1, the description is directed to an example of aninformation recording medium according to the present invention.

FIG. 1 shows a partial sectional view of an information recording medium10 according to Embodiment 1. The information recording medium 10includes: a substrate 11; a first protective layer 12 a, a firstinterface layer 13 a, a recording layer 14, a second interface layer 13b, a second protective layer 12 b, an optical absorption compensationlayer 15, and a reflective layer 16, which are laminated sequentially onthe substrate 11; and a dummy substrate 18 bonded to the reflectivelayer 16 with an adhesive layer 17. In other words, the informationrecording medium 10 is provided with the substrate 11 and the recordinglayer 14 disposed above the substrate 11. The information recordingmedium 10 is irradiated with energy beams (generally, laser beams) 19for recording and reproduction from the substrate 11 side.

The recording layer 14 is transformed in phase reversibly between acrystal phase and an amorphous phase by the irradiation of the energybeams 19. Specifically, an irradiation of a high power energy beam 19allows a crystal phase portion of the recording layer 14 to change to anamorphous phase. An irradiation of a low power energy beam 19 allows anamorphous phase portion of the recording layer 14 to change to a crystalphase. Preferably, the recording layer 14 has a thickness of 5 nm to 15nm.

The recording layer 14 contains, as constituent elements, Ge, Sb, Te,Sn, and at least one element M selected from Ag, Al, Cr, Mn, and N.Specifically, materials can be used that are expressed by a compositionformula of[(Ge, Sn)_(A)Sb₂Te_(3+A)]_(100−B)M_(B),wherein 0<A≦10 and 0<B≦20. This composition formula indicates that Geand Sn are contained in a total amount of [(100−B)·A]/(2A+5) atom. % inthe recording layer 14. It is more preferable that A and B satisfy 2≦A≦8and 2≦B≦15, respectively. In the materials expressed by this compositionformula, it is preferable that the Sn content is 2 atom. % to 20 atom.%.

The materials expressed by the above-mentioned composition formula canbe defined as materials prepared by substitution of part of Ge in aGeTe—Sb₂Te₃ pseudobinary composition by Sn and addition of an element Mthereto. The GeTe—Sb₂Te₃ pseudobinary composition has been used as amaterial with a high crystallization rate. In this material, SnTe orPbTe is solved, so that the crystallization rate further can beincreased. Both SnTe and PbTe have a rock-salt crystal structure likethe GeTe—Sb₂Te₃ pseudobinary. In addition, SnTe and PbTe have highcrystallization rates and are solved with Ge—Sb—Te easily. Particularly,SnTe is preferable as a material to be solved in a GeTe—Sb₂Te₃pseudobinary composition.

For instance, it is preferred to use GeTe—SnTe—Sb₂Te₃, which can beobtained by the mixture of SnTe with GeTe—Sb₂Te₃ pseudobinarycomposition, as the material of the recording layer 14. In this case,when part of Ge is substituted by Sn and thus (Ge,Sn)Te—Sb₂Te₃ isobtained, the crystallization rate further increases.

The element M contained in the recording layer 14 is considered ashaving a function of suppressing the atom movement. The use of twoelements of Al and Ag, Cr and Ag, or Mn and Ag as the element M canimprove the repeated-rewriting performance, suppress the deteriorationin crystallization sensitivity with time, and increase a signalamplitude. However, when the concentration of the element M or thenumber of elements is to be increased, it is preferred to increase theSn concentration in the recording layer 14 to prevent thecrystallization rate from being reduced. Preferably, the concentrationof the element M is equal to or lower than the Sn concentration.

The substrate 11 is a disc-like transparent substrate. As the materialof the substrate 11, for example, resins such as amorphous polyolefin orpolymethyl methacrylate (PMMA) or glass can be used. At the surface ofthe substrate 11 on the recording layer 14 side, guide grooves forguiding the energy beams 19 may be formed. The surface of the substrate11 on the energy beam 19 incident side is smooth and flat in general.The substrate has a thickness of, for instance, about 0.5 mm to 1.3 mm.

The first and second protective layers 12 a and 12 b have a function ofprotecting the recording layer 14. The thicknesses of the first andsecond protective layers 12 a and 12 b are adjusted, so that thequantity of incident light on the recording layer 14 can be increasedand the signal amplitude (the variation in quantity of reflected lightbefore and after recording) also can be increased. The thickness of theprotective layers can be determined by calculation based on, forexample, a matrix method (see, for instance, Chapter 3 in “Wave Optics”by Hiroshi Kubota, published by Iwanami Shinsho, 1971). With thiscalculation, the thickness of the protective layers can be determined sothat a considerable difference is obtained between the quantity of thelight reflected from the recording layer 14 in a crystalline state andthat reflected from the recording layer 14 in an amorphous state and sothat the quantity of incident light on the recording layer 14 isincreased.

The first and second protective layers 12 a and 12 b are formed of, forexample, dielectrics. Specifically, materials used for the first andsecond protective layers 12 a and 12 b include oxides such as SiO₂ andTa₂O₅, nitrides such as Si—N, Al—N, Ti—N, Ta—N, Zr—N, or Ge—N, sulfidessuch as ZnS, or carbides such as SiC. In addition, mixtures of suchmaterials also can be used. Among them, ZnS—SiO₂ as a mixture of ZnS andSiO₂ is a particularly good material. The mixture ZnS—SiO₂ is anamorphous material, has a high refractive index, and is excellent inmechanical properties and moisture resistance. Furthermore, the mixtureZnS—SiO₂ can be deposited at a high deposition rate. The first andsecond protective layers 12 a and 12 b may be formed of the samematerial or different materials.

The first and second interface layers 13 a and 13 b are disposed betweenthe first protective layer 12 a and the recording layer 14 and betweenthe second protective layer 12 b and the recording layer 14,respectively. The first and second interface layers 13 a and 13 b have afunction of preventing material migration occurring between the firstprotective layer 12 a and the recording layer 14 and between the secondprotective layer 12 b and the recording layer 14. Materials that can beused for the first and second interface layers 13 a and 13 b include,for example, nitrides such as Si—N, Al—N, Zr—N, Ti—N, Ge—N, or Ta—N,nitride oxides containing them, or carbide such as SiC. In order toobtain excellent recording/erasing performance, preferably, the firstand second interface layers 13 a and 13 b have a thickness in the rangeof 1 nm to 10 nm, and more preferably in the range of 2 nm to 5 nm.

In the optical absorption compensation layer 15, the ratio of theoptical absorptance when the recording layer 14 is in a crystallinestate to that when the recording layer 14 is in an amorphous state isadjusted. The optical absorption compensation layer 15 can preventrecording mark shapes from being distorted in rewriting. It is preferredto use a material having a high refractive index and absorbing lightappropriately as the material of the optical absorption compensationlayer 15. For instance, a material with a refractive index n of 3 to 6and an extinction coefficient k of 1 to 4 can be used. Specifically, anamorphous Ge alloy such as Ge—Cr or Ge—Mo, or an amorphous Si alloy suchas Si—Cr, Si—Mo, or Si—W can be used. In addition, it also is possibleto use crystalline metal, semi-metal, or a semiconductor material, suchas a Si alloy, a telluride, Ti, Zr, Nb, Ta, Cr, Mo, W, SnTe, or PbTe.

The reflective layer 16 has a function of increasing the quantity oflight to be absorbed in the recording layer 14. In addition, theformation of the reflective layer 16 allows heat generated in therecording layer 14 to be diffused quickly to facilitate thetransformation in phase of the recording layer 14 to the amorphousphase. Furthermore, when the reflective layer 16 is formed, laminatedlayers can be protected from an operating environment.

A single-element metal with high thermal conductivity such as, forexample, Al, Au, Ag, or Cu, can be used as the material of thereflective layer 16. Alloys also may be used, including Al—Cr, Al—Ti,Ag—Pd, Ag—Pd—Cu, Ag—Pd—Ti, or the like. In such alloys, theircompositions are varied, so that the moisture resistance and thermalconductivity can be adjusted. Furthermore, it may be possible to omitthe reflective layer 16 depending on the material of the recording layer14 and information recording conditions.

The adhesive layer 17 is used for bonding the dummy substrate 18 to thereflective layer 16. The adhesive layer 17 is formed of a material witha high thermal resistance and high adhesiveness. For example, resinssuch as ultraviolet curable resins or the like can be used for theadhesive layer 17. Specifically, a material containing acrylic resin orepoxy resin as a main component can be used. The adhesive layer 17 alsomay be formed using a resin film, a dielectric film, a double sided tapeor combinations thereof

The dummy substrate 18 is a disc-like substrate. The dummy substrate 18has a function of improving the mechanical strength of the informationrecording medium 10. The dummy substrate 18 protects the laminatedlayers. The materials described with respect to the substrate 11 can beused for the dummy substrate 18. The material of the dummy substrate 18may be the same as or different from that of the substrate 11. Inaddition, the thickness of the dummy substrate 18 may be the same as ordifferent from that of the substrate 11.

In the information recording medium 10 according to Embodiment 1, therecording layer 14 contains the elements M, Ge, Sb, Te, and Sn asconstituent elements. According to the information recording medium 10,therefore, an information recording medium can be obtained that allowshigh density recording to be carried out, is excellent in therepeated-rewriting performance, and is deteriorated less incrystallization sensitivity with time.

In Embodiment 1, the information recording medium 10 with one recordinglayer 14 was described. However, the information recording medium of thepresent invention may be provided with two recording layers 14 (the sameholds true in the following embodiments). For example, two informationrecording media 10 are laminated using an adhesive layer with theirrespective dummy substrates 18 adhering to each other, so that atwo-sided information recording medium can be obtained.

Embodiment 2

In Embodiment 2, another example of an information recording medium ofthe present invention is described. The same portions as those describedin Embodiment 1 are indicated with the same numerals and the duplicatedescriptions will be omitted (the same holds true in the followingembodiment).

FIG. 2 shows a partial sectional view of an information recording medium20 according to Embodiment 2. The information recording medium 20includes: a first substrate 21; a reflective layer 16, an opticalabsorption compensation layer 15, a second protective layer 12 b, asecond interface layer 13 b, a recording layer 14, a first interfacelayer 13 a, and a first protective layer 12 a, which are laminatedsequentially on the first substrate 21; and a second substrate 22 bondedto the first protective layer 12 a with an adhesive layer 17. In otherwords, the information recording medium 20 is provided with the firstsubstrate 21 and the recording layer 14 disposed above the firstsubstrate 21. The information recording medium 20 is irradiated withenergy beams (generally, laser beams) 19 for recording and reproductionfrom the second substrate 22 side.

The same substrate as the substrate 11 can be used for the firstsubstrate 21. The second substrate is a transparent disc-like substrateand can be formed of the same material as that of the substrate 11. Atthe surface of the second substrate 22 on the recording layer 14 side,guide grooves for guiding the energy beams 19 may be formed.Particularly, it is preferable that the surface of the second substrate22 on the energy beam 19 incident side is smooth and flat. The secondsubstrate 22 is thinner than the first substrate 21 and has a thicknessof, for example, about 0.05 mm to 0.5 mm.

In the information recording medium 20, since the second substrate 22 isthinner than the first substrate 21, the numerical aperture of anobjective lens can be increased. In this case, a beam spot size w can begiven by:w=k·λ/NA,wherein λ denotes a wavelength of the energy beams 19, NA represents thenumerical aperture of the objective lens, and k is a constant. The spotsize w is reduced with the decrease in the wavelength and with increasein the numerical aperture NA. Therefore, in the information recordingmedium 20 allowing the numerical aperture of the objective lens to beincreased, higher density recording is possible as compared to the caseof the information recording medium 10. It has been reported that, forinstance, an objective lens with a NA of 0.6 can be used when thesubstrate has a thickness of 0.6 mm, and an objective lens with a NA of0.85 can be used when the substrate has a thickness of 0.1 mm (KiyoshiOsato, “A Rewritable Optical Disk System with over 10GB of Capacity”,Proc. SPIE. Optical Data Storage'98, 3401, 80-86 (1998)).

In the information recording medium 20, the recording layer 14 made ofthe material described with respect to the information recording medium10 is used, so that the same effect as in the information recordingmedium 10 can be obtained.

Embodiment 3

In Embodiment 3, a method of manufacturing an information recordingmedium 10 is described as an example of a method according to thepresent invention. As described below, the manufacturing methodaccording to Embodiment 3 includes a step of forming a recording layer14 by a vapor deposition method.

First, a substrate 11 is prepared and is placed in deposition equipment.Single wafer deposition equipment with one power source in one vacuumchamber or in-line deposition equipment with a plurality of powersources in one vacuum chamber can be employed as the depositionequipment used in Embodiment 3. The following respective layers may bedeposited using the same or different deposition equipment.

A first protective layer 12 a, a first interface layer 13 a, a recordinglayer 14, a second interface layer 13 b, a second protective layer 12 b,an optical absorption compensation layer 15, and a reflective layer 16are formed sequentially on the substrate 11. When grooves for guidingenergy beams 19 are formed at the surface of the substrate 11, the firstprotective layer 12 a is formed on the surface with the grooves.

The first protective layer 12 a, the first interface layer 13 a, thesecond interface layer 13 b, and the second protective layer 12 b can beformed by, for instance, a sputtering method. Specifically, a basematerial made of a compound may be sputtered in an Ar gas atmosphere oran atmosphere of a gas mixture of an Ar gas and a reactant gas. Areactive sputtering method also may be used in which a base materialmade of metal is sputtered in an atmosphere of a gas mixture of an Argas and a reactant gas.

The recording layer 14 is made of the material described in Embodiment 1and is formed by a vapor deposition method. At least one selected from avacuum evaporation method, a sputtering method, an ion plating method, achemical vapor deposition, and a molecular beam epitaxy can be used asthe vapor deposition method.

For example, the recording layer 14 can be formed by a sputtering methodusing a gas mixture containing at least one gas selected from nitrogengas and oxygen gas and one rare gas selected from argon and krypton.Examples of the gas mixture include a gas mixture of nitrogen gas andargon, a gas mixture of nitrogen gas and krypton, or gas mixturescontaining oxygen gas added thereto. Specifically, a base material(target) containing Ge, Sb, Te, Sn, and an element M is sputtered in thegas mixture atmosphere described above, so that the recording layer 14can be formed. Five base materials corresponding to Ge, Sb, Te, Sn, andthe element M, respectively, or a binary or ternary base materialobtained by combination of some elements may be used as the basematerial. When the element M consists of nitrogen alone, a targetcontaining Ge, Sb, Te, and Sn is sputtered in an atmosphere containingnitrogen gas, so that the recording layer 14 can be formed.

The sputtering method allows easy formation of a recording layerexpressed by[(Ge, Sn)_(A)Sb₂Te_(3+A)]_(100−B)M_(B),wherein 0<A≦10 and 0<B≦20.

Preferably, the recording layer 14 is deposited at a deposition rate of0.5 nm/sec to 5 nm/sec (more preferably, 0.8 nm/sec to 3 nm/sec).

After the formation of the second protective layer 12 b, the opticalabsorption compensation layer 15 and the reflective layer 16 are formedon the second protective layer 12 b. The optical absorption compensationlayer 15 and the reflective layer 16 can be formed by sputtering of basematerials made of metals in an Ar gas atmosphere.

Next, the adhesive layer 17 is formed on the reflective layer 16 and thereflective layer 16 and the dummy substrate 18 are bonded to each other.Thus, the information recording medium 10 can be manufactured. Aninitialization step for crystallizing the whole recording layer 14 maybe carried out as required. The initialization step can be carried outbefore or after the dummy substrate 18 is bonded.

The information recording medium 20 also can be manufactured by the samemethod as in the case of the information recording medium 10. Therespective layers of the information recording medium 20 can be formedby the same methods as in the case of the information recording medium10. Furthermore, the second substrate 22 can be bonded to the firstprotective layer 12 a with the adhesive layer 17 as in the case of thedummy substrate 18. Similarly in the method of manufacturing theinformation recording medium 20, the initialization step is carried outas required. The initialization step can be carried out before or afterthe second substrate 22 is bonded. In the information recording medium20, the energy beams 19 are incident on the second substrate side 22,and therefore it is preferable that the thickness of the adhesive layer17 is uniform throughout.

According to the manufacturing method of Embodiment 3, informationrecording media of the present invention can be manufactured easily.

EXAMPLES

The present invention is described further in detail using examples asfollows.

Example 1

In Example 1, an example of the information recording medium 10 isdescribed. The following description is directed to a method ofmanufacturing an information recording medium according to Example 1.

First, a polycarbonate substrate (with a thickness of 0.6 mm) with aspiral guide groove formed at its one surface was prepared as thesubstrate 11. A ZnS—SiO₂ layer (the first protective layer 12 a, with athickness of 140 nm), a Ge—N layer (the first interface layer 13 a, witha thickness of 5 nm), a recording layer (the recording layer 14), a Ge—Nlayer (the second interface layer 13 b, with a thickness of 3 nm), aZnS—SiO₂ layer (the second protective layer 12 b, with a thickness of 40nm), a GeCr layer (the optical absorption compensation layer 15, with athickness of 40 nm), and a Ag alloy layer (the reflective layer 16, witha thickness of 80 nm) were formed sequentially on the polycarbonatesubstrate by the sputtering method. The thicknesses of the firstprotective layer 12 a and the second protective layer 12 b were adjustedso that a larger signal amplitude (variation in quantity of reflectedlight) in a wavelength of 660 nm and a larger quantity of incident lighton the recording layer can be obtained. These thicknesses weredetermined using the calculation based on the matrix method.

The recording layer was formed using a material expressed by acomposition formula of [(Ge, Sn)₄Sb₂Te₇]₉₅N₅. This recording layercontains Ge and Sn in a total amount of 95×4/(4+2+7)≦29 atom. %.Specifically, the Ge content and the Sn content were set to be 24 atom.% and 5 atom. %, respectively.

Afterward, an ultraviolet curable resin was spin-coated on the Ag alloylayer to form the adhesive layer 17. Finally, a dummy substrate (with athickness of 0.6 mm) was allowed to adhere to the Ag alloy layer, whichthen was irradiated with ultraviolet rays. Thus, the Ag alloy layer andthe dummy substrate were bonded.

In Example 1, the whole information recording medium was irradiated withthe laser beams after the dummy substrate was bonded, so that the wholerecording layer was crystallized. Thus, an information recording mediumaccording to Example 1 was produced. In Example 1, eight types ofinformation recording media 10-11 to 10-18 having recording layers withdifferent thicknesses were produced.

On the other hand, information recording media were produced ascomparative examples in the same manner as in the above-mentionedexample except that the materials of the recording layers were changed.In these comparative examples, the recording layers were formed with amaterial expressed by a composition formula of Ge₄Sb₂Te₇. Similarly inthe comparative examples, eight types of information recording mediaC-11 to C-18 having the recording layers with different thicknesses wereproduced.

With respect to the above-mentioned 16 types of information recordingmedia, the repeated-rewriting performance and the deterioration incrystallization sensitivity with time were evaluated. The methods ofevaluating them are described later. The evaluation results are shown inTable 1.

TABLE 1 Information Thickness Variation in Jitter Recording of RecordingLayer Rewritable Value Medium No. [nm] Number of Times [%] 10-11 3 E1 E210-12 5 C1 C2 10-13 7 A1 B2 10-14 9 A1 B2 10-15 11 B1 A2 10-16 13 B1 A210-17 15 C1 A2 10-18 17 C1 A2 C-11 3 E1 E2 C-12 5 E1 E2 C-13 7 B1 D2C-14 9 B1 D2 C-15 11 C1 C2 C-16 13 C1 C2 C-17 15 D1 B2 C-18 17 D1 B2200000 ≦ A1 0 ≦ A2 < 1 100000 ≦ B1 < 200000 1 ≦ B2 ≦ 2 10000 ≦ C1 <100000 2 < C2 < 3 D1 < 10000 3 ≦ D2 E1: Unrewritable E2: Unevaluable

In Table 1, larger “Rewritable Number of Times” indicates betterrepeated-rewriting performance. A1 to D1 represent the ranges describedin the bottom of Table 1, respectively. E1 denotes that no rewriting waspossible. In Table 1, smaller “Variation in Jitter Value” indicates lessdeterioration in crystallization sensitivity with time. A2 to D2represent the ranges described in the bottom of Table 1. E2 denotes thatno evaluation was possible because the jitter values before a shelf testexceeded 13% both between leading edges of recording marks and betweenend edges of the recording marks. A1 to E1 and A2 to E2 in the followingtables also indicate the same meanings as in the above.

As shown in Table 1, none of the information recording media C-11 toC-18 of the comparative examples showed the characteristics A or B bothin the rewritable number of times and variation in jitter value. On theother hand, the information recording media 10-13 to 10-16 of Example 1showed the characteristics A or B both in the rewritable number of timesand variation in jitter value.

On the average, the information recording media of Example 1 wereexcellent in the repeated-rewriting performance and were lessdeteriorated in crystallization sensitivity with time as compared to thecomparative examples C-11 to C-18. It is conceivable that theimprovement in the repeated-rewriting performance resulted from theaddition of nitrogen. In addition, it also is conceivable that thedeterioration in crystallization sensitivity with time was suppressedbecause of the increase in crystallization rate due to the substitutionof part of Ge in Ge₄Sb₂Te₇ by Sn.

Example 2

In Example 2, the description is directed to an example in which theinformation recording medium 10 was produced with the Sn content in therecording layer being varied.

Information recording media were produced as in Example 1 except thatthe thickness of the recording layers was set to be 7 nm and the Sncontents in the recording layers were varied. In the informationrecording media of Example 2, the recording layers were formed using amaterial expressed by a composition formula of [(Ge, Sn)₄Sb₂Te₇]₉₅N₅.Eight types of information recording media 10-21 to 10-28 were producedwith the Sn content varied between 2 atom. % to 25 atom. % and the Gecontent varied between 27 atom. % to 4 atom. %. The informationrecording medium 10-22 is identical with the information recordingmedium 10-13. In addition, an information recording medium C-21 that isfree from Sn also was produced as a comparative example.

With respect to the information recording media 10-21 to 28 and C-21,the variations in jitter value were measured by the method describedlater and thus the deterioration in crystallization sensitivity withtime was evaluated. The evaluation results are shown in Table 2.

TABLE 2 Information Ge/Sn Contents Recording in Recording Layer MediumNo. Ge[atom. %] Sn[atom. %] Variation in Jitter Value [%] 10-21 27 2 C210-22 24 5 B2 10-23 22 7 B2 10-24 19 10 A2 10-25 14 15 A2 10-26 9 20 A210-27 6 23 E2 10-28 4 25 E2 C-21 29 0 D2

As shown in Table 2, excellent characteristics were obtained when the Sncontent was in the range between 2 atom. % and 20 atom. %.

Example 3

In Example 3, the description is directed to an example in which theinformation recording medium 10 was produced with the element M beingvaried.

Information recording media were produced as in Example 1 except thatthe element M was varied and the thickness of the recording layers wasset to be 11 nm. In the information recording media of Example 3, therecording layers were formed using a material expressed by a compositionformula of [(Ge, Sn)₄Sb₂Te₇]₉₅M₅. The Ge content was set to be 24 atom.% and the Sn content to be 5 atom. %. In Example 3, five types ofinformation recording media 10-31 to 10-35 were produced using Mn, Ag,Cr, Al, or N as the element M. In addition, an information recordingmedium C-31 that is free from the element M also was produced as acomparative example.

With respect to the information recording media 10-31 to 35 and C-31,the repeated-rewriting performance was evaluated by the method describedlater. The evaluation results are shown in Table 3.

TABLE 3 Information Recording Rewritable Medium No. Element M Number ofTimes 10-31 Mn 150000 10-32 Ag 90000 10-33 Cr 160000 10-34 Al 18000010-35 N 150000 C-31 None 70000

As shown in Table 3, the use of Mn, Ag, Cr, Al, or N as the element Mallowed the rewriting performance to improve. This effect was quitelarge, particularly when Mn, Cr, Al, or N was used. In addition, when Agwas used as the element M, the signal amplitude increased and thus thejitter values between leading edges of recording marks and between endedges of the recording marks were increased.

Example 4

In Example 4, the description is directed to an example in which theinformation recording medium 10 was produced using Mn as the element M.

Information recording media were produced as in Example 1 except forusing Mn as the element M. In the information recording media of Example4, the recording layers were formed using a material expressed by acomposition formula of [(Ge, Sn)₄Sb₂Te₇]₉₅Mn₅. The Ge content was set tobe 24 atom. % and the Sn content to be 5 atom. %. In Example 4, eighttypes of information recording media 10-41 to 10-48 were produced withthe recording layers having different thicknesses.

With respect to the information recording media 10-41 to 10-48, therepeated-rewriting performance and the deterioration in crystallizationsensitivity with time were evaluated by the methods described later. Theevaluation results are shown in Table 4.

TABLE 4 Information Thickness Recording of Recording Layer RewritableVariation in Jitter Medium No. [nm] Number of Times Value [%] 10-41 3 E1E2 10-42 5 C1 C2 10-43 7 A1 B2 10-44 9 B1 B2 10-45 11 B1 A2 10-46 13 B1A2 10-47 15 C1 A2 10-48 17 D1 A2

As shown in Table 4, the use of Mn as the element M allowed informationrecording media to be obtained which were excellent in therepeated-rewriting performance and were deteriorated less incrystallization sensitivity with time. Particularly, these twocharacteristics were excellent when the thickness of the recording layerwas 7 nm to 13 nm. In addition, random signals recorded before theleave-standing step were reproduced without the variation in jittervalue. As a result, it was confirmed that there also was no problem inarchival property.

Example 5

In Example 5, the description is directed to an example in which theinformation recording medium 10 was produced with the content of theelement M and the Sn content being varied.

Information recording media were produced as in Example 1 except that Crwas used as the element M and the Sn content was varied. The recordinglayers were formed using a material expressed by a composition formulaof [(Ge, Sn)₄Sb₂Te₇]₉₅Cr₅. The Sn content was varied from 0 atom. % to25 atom. % and the Ge content from 29 atom. % to 4 atom. %. Thethickness of the recording layer was set to be 9 nm.

With respect to a plurality of information recording media thusproduced, the repeated-rewriting performance and the deterioration incrystallization sensitivity with time were evaluated by the methodsdescribed later. The ranges in which particularly excellent results werenoted as a result of the evaluations were indicated by the mark * inTable 5.

TABLE 5 Cr Content Sn Content [atom. %] [atom. %] 0 2 5 7 10 15 20 23 250 2 * * * * 5 * * * * 7 * * * 10 * * 15 * 20 23 25

The mark * denotes that the rewritable number of times was at least100000 and the variation in jitter value was not more than +2%. As shownin Table 5, the use of a material containing 5 atom. % to 20 atom. % Snand 2 atom. % to 15 atom. % Cr allowed information recording media to beobtained which were excellent in the repeated-rewriting performance andwere deteriorated less in crystallization sensitivity with time.

In addition, the same test was carried out using Mn or Al as the elementM. As a result, the same results were obtained as in the informationrecording media using Cr as the element M.

Furthermore, the same test was carried out using Ag and Mn, Ag and Al,or Ag and Cr as the element M. The Ag content was set to be 1 atom. %.As a result, information recording media with excellent characteristicswere obtained when the Sn content was set to be 5 atom. % to 20 atom. %and the content of Mn, Al, or Cr 1 atom. % to 13 atom. %.

Example 6

The description in Example 6 is directed to an example in which theinformation recording medium 20 was produced.

First, a polycarbonate substrate (with a thickness of 1.1 mm) with aspiral guide groove formed at its one surface was prepared as the firstsubstrate 21. Then, a Ag alloy layer (the reflective layer 16, with athickness of 80 nm), a Te compound layer (the optical absorptioncompensation layer 15, with a thickness of 20 nm), a ZnS—SiO₂ layer (thesecond protective layer 12 b, with a thickness of 11 nm), a Ge—N layer(the second interface layer 13 b, with a thickness of 3 nm), a recordinglayer (the recording layer 14), a Ge—N layer (the first interface layer13 a, with a thickness of 5 nm), and a ZnS—SiO₂ layer (the firstprotective layer 12 a, with a thickness of 60 nm) were formedsequentially on the polycarbonate substrate by the sputtering method.The thicknesses of the first protective layer 12 a and the secondprotective layer 12 b were adjusted so that a larger signal amplitude(variation in quantity of reflected light) in a wavelength of 405 nm anda larger quantity of incident light on the recording layer wereobtained. These thicknesses were determined using the calculation basedon the matrix method.

The recording layer was formed using a material expressed by acomposition formula of [(Ge, Sn)₄Sb₂Te₇]₉₅Mn₅. The Ge and Sn contentswere set to be 19 atom. % and 10 atom. %, respectively.

Afterward, an ultraviolet curable resin was applied to the firstprotective layer to form the adhesive layer 17. Finally, a secondsubstrate (the second substrate 22, with a thickness of 0.1 mm) wasallowed to adhere to the first protective layer, which then wasirradiated with ultraviolet rays. Thus, the first protective layer andthe second substrate were bonded.

In Example 6, after the second substrate was bonded, the wholeinformation recording medium was irradiated with laser beams, so thatthe whole recording layer was crystallized. Thus, an informationrecording medium according to Example 6 was produced. In Example 6,seven types of information recording media 20-1 to 20-7 having recordinglayers with different thicknesses were produced. With respect to theseinformation recording media, the repeated-rewriting performance and thedeterioration in crystallization sensitivity with time were evaluated bythe evaluation methods described later. In Example 6, high densityrecording was carried out using laser beams with a wavelength of 405 nmand an objective lens with a NA of 0.8 and thus the characteristics wereevaluated. The evaluation results are shown in Table 1.

TABLE 6 Information Thickness Recording of Recording Layer RewritableVariation in Jitter Medium No. [nm] Number of Times Value [%] 20-1 5 E1E2 20-2 7 B1 C2 20-3 9 B1 B2 20-4 11 B1 B2 20-5 13 B1 B2 20-6 15 C1 B220-7 17 E1 E2

As shown in Table 6, it was possible to obtain information recordingmedia that were excellent in repeated-rewriting performance and weredeteriorated less in crystallization sensitivity with time in highdensity recording. It is conceivable that this is because part of Ge ofGe₄Sb₂Te₇ was substituted by Sn and Mn was added as the element M.

In addition, the same test was carried out using Cr or Al as the elementM and the same results were obtained as in the information recordingmedia produced using Mn as the element M.

Moreover, the same test was carried out using Ag and Mn, Ag and Al, orAg and Cr as the element M. The Ag content was set to be 1 atom. %. Thecontent of Mn, Al, or Cr was set to be 4 atom. %. As a result, the sameresults were obtained as in the information recording media producedusing Mn as the element M.

Evaluation of Repeated-Rewriting Performance

The following description is directed to a method of evaluating therepeated-rewriting performance.

FIG. 3 shows a schematic view of a recording/reproducing device used forthe evaluation. The recording/reproducing device includes a spindlemotor 32 for revolving an information recording medium 31, an opticalhead 34 provided with a semiconductor laser 33, and an objective lens35. Laser beams 36 emitted from the semiconductor laser 33 are convergedby the objective lens 35 and a recording layer of the informationrecording medium 31 is irradiated therewith. The information recordingmedia produced in the examples are used as the information recordingmedium 31.

In the evaluations in Examples 1 to 5, a semiconductor laser 33 with awavelength of 660 nm and an objective lens 35 with a numerical apertureof 0.6 were used, and the linear velocity was set to be 8.2 m/sec. Inthe evaluation in Example 6, a semiconductor laser 33 with a wavelengthof 405 nm and an objective lens 35 with a numerical aperture of 0.8 wereused, and the linear velocity was set to be 8.6 m/sec.

For the evaluation of the repeated-rewriting performance, random signalswere recorded while the laser beams 36 were modulated to have a highoutput peak power Pp and a low output bias power Pb. Then, the jittervalue between leading edges of recording marks and that between endedges of the recording marks were measured, and they were averaged.Thus, the mean jitter value was calculated. The repeated-rewritingperformance was evaluated in terms of the rewriting number of times (therewritable number of times in the tables) before the mean jitter valuereached 13% when signals were recorded repeatedly using the laser beams36 with Pp and Pb. When the information recording medium is to be usedas an external memory of a computer, the preferable rewritable number oftimes is at least 100000. When the information recording medium is to beused as an image/voice recorder, the rewritable number of times of 10000is considered as being sufficient.

Evaluation of Deterioration in Crystallization Sensitivity with Time

The following description is directed to a method of evaluating thedeterioration in crystallization sensitivity with time.

Initially, random signals were recorded on an information recordingmedium ten times by the same method as in the evaluation of therepeated-rewriting performance, and the jitter value between leadingedges of recording marks and that between end edges of the recordingmarks were measured.

Next, the information recording medium was left in an environment with atemperature of 90° C. and a relative humidity of 20% for 24 hours (aleave-standing step). Afterward, the signals recorded before theleave-standing step were overwritten by random signals once. Then, thejitter value between leading edges of recording marks and that betweenend edges of the recording marks were measured.

The “Variation in Jitter Value [%]” in the tables is given by (Variationin Jitter Value [%])≦(Jitter Value After Leave-Standing Step[%])—(Jitter Value Before Leave-Standing Step [%]).

When the crystallization sensitivity does not vary before and after theleave-standing step, the variation in jitter value hardly occurs. On thecontrary, when the crystallization sensitivity decreases after theleave-standing step, the variation in jitter value increases. Therefore,it can be understood that the less the jitter value varies, the less thecrystallization sensitivity is deteriorated with time. Practically, itis preferable that the worse one of the variations in jitter valuebetween leading edges and end edges is not more than +2%.

The invention may be embodied in other forms without departing from thespirit or essential characteristics thereof. The embodiments disclosedin this application are to be considered in all respects as illustrativeand not limiting. The scope of the invention is indicated by theappended claims rather than by the foregoing description, and allchanges which come within the meaning and range of equivalency of theclaims are intended to be embraced therein.

1. A method of manufacturing an information recording medium including asubstrate and a recording layer disposed above the substrate, the methodcomprising forming the recording layer by a vapor deposition method,wherein the recording layer comprises, as constituent elements, Ge, Sb,Te, Sn, and at least one element M selected from Ag, Al, Cr, Mn, and Nand is transformed in phase reversibly between a crystal phase and anamorphous phase by an irradiation of an energy beam, and the recordinglayer is formed of a material expressed by a composition formula of[(Ge, Sn)_(A)Sb₂Te_(3+A)]_(100−B)M_(B), where 0<A≦10, 0<B≦20, such thatA and B each represent an atomic percent and M is at least one of Ag,Al, Cr, Mn or N.
 2. The method of manufacturing an information recordingmedium according to claim 1, wherein the vapor deposition method is atleast one method selected from a vacuum evaporation method, a sputteringmethod, an ion plating method, a chemical vapor deposition, and amolecular beam epitaxy.
 3. The method of manufacturing an informationrecording medium according to claim 1, wherein the vapor depositionmethod is a sputtering method using a gas comprising at least one gasselected from nitrogen gas and oxygen gas and one rare gas selected fromargon and krypton.
 4. The method of manufacturing an informationrecording medium according to claim 1, wherein the recording layer isdeposited at a deposition rate of 0.5 nm/sec to 5 nm/sec.
 5. The methodof manufacturing an information recording medium according to claim 1,wherein the recording layer has a thickness of 5 nm to 15 nm.